Amidothiol phosphoric acid esters

ABSTRACT

Amidothiol phosphoric acid esters having the formula,   WHEREIN R1 is methyl, ethyl or propyl, R2 is a C3-C10 alkenyl, a C2-C10 alkylthioalkyl, a C2-C10 alkoxyalkyl or a C2-C10 cyanoalkyl, and A is a C1-C3 alkyl, a C3-C6 alkenyl, a C3-C6 alkinyl, a halogen-substituted C3-C6 alkenyl or a halogensubstituted C3-C6 alkinyl, which are used as an active ingredient of a pest controlling composition with a systemic action.

United States Patent [191 Fujimoto et al.

[ Mar. 26, 1974 22 Filed: Oct. 12, 1970 21 Appl. No.: 80,224

[30] Foreign Application Priority Data Oct. 23, 1969 Japan 44-85059 [52]US. Cl.....;..- 260/940, 260/948, 260/950, 260/956, 260/957, 260/979,260/987,

[51] Int. Cl. A0ln 9/36, C07f 9/24 [58] Field of Search 260/940, 950,948, 956, 260/957, 959

[56] References Cited FOREIGN PATENTS OR APPLICATIONS France 260/959Primary Examiner-Lorraine A. Weinberger Assistant Examiner-Richard L.Raymond Attorney, Agent, or Firm-Stevens, Davis, Miller & Mosher [5 7]ABSTRACT Amidothiol phosphoric acid esters having the formula,

wherein R is methyl, ethyl or propyl, R is a C ,C alkenyl, a C Calkylthioalkyl, a C C alkoxyalkyl or a C C cyanoalkyl, and A is a C,-Calkyl, a C,,C alkenyl, a C C alkinyl, a halogen-substituted C C alkenylor a halogen-substituted C -C alkinyl, which are used as an activeingredient of a pest controlling composition with a systemic action.

13 Claims, N0 Drawings AMIDOTHIOL PHOSPHORIC ACID ESTERS This inventionrelates to a novel amidothiol phosphoric acid ester, to a process forpreparing the same and to a composition containing the same.

More particularly, the invention pertains to a novel amidothiolphosphoric acid ester represented by the formula (I),

H (II) wherein R, and R are as defined above, with an alkalihydrosulfide represented by the formula (III),

MSI-l (Ill) wherein M is an alkali metal, to form a phosphoric acid saltrepresented by the formula (IV),

M H P wherein R R and M are as defined above, and condensing saidphosphoric acid salt with a halogen compound represented by the formula(V),

Hal A wherein Hal is a halogen atom, and A is as defined above.

The present compounds represented by the formula (I) are particularlysuitable for the control of pests in agriculture, forestry andlive-stock, and can most effectively control plant-hoppers, mites,aphids, stem borers, rice stem borers, lady beetles, scales andnematodes. Further, the present compounds have effects on such insectsas Lepidoptera, Diptera, Coleoptera, Hemiptera and Orthoptera, and onarthropods, molluscs, filamentous fungi and bacteria. What is to beparticularly mentioned is that the present compounds characteristicallyhave a so-called systemic action. Systemic chemicals are classified, ingeneral, into those which have such property as to merely permeate intothe hodies of platns and animals and those which have such property asto move after permeation, but the present compounds have both of thesaid properties. Further, common insecticides are used in order todirectly kill injurious insects, but the present compounds have suchphysiological actions that when used at less than lethal concentrations,the compounds disturb the metamorphosis of pests and decrease the numberof eggs laid by the pests to disturb the normal propagation thereof. Inaddition, the present compounds have excellent contact-pesticidalactions and show marked insecticidal and miticidal action against pestswhich are resistant to conventional chemicals.

Heretofore, there are a few reports on phosphoric acid esters similar tothe present compounds. Japanese Patent Publication No. 27,356/68discloses O-alkyl-S- alkyl-N-phenyl phosphorothioamidates, and Chemistryand Industry, May 6, 196], discloses on page 591O-alkyl-S-alkyl-N-cycloalkyl phosphorothioamidates, but these compoundshave low insecticidal activities shown below in the test examples.Japanese Patent Publication No. 14,525/67 discloses O-alkyl-S-methylphosphorothioamidates, but it is apparent from the test examples shownbelow that these compounds are extremely high in toxicity towarm-blooded animals. It has been found that the present compounds arenot only high in insecticidal activity but also low in toxicity towarm-blooded animals. Accordingly, the present compounds are quiteexcellent compounds which can be used safely without any injury tomammals. Further, they are excellent compounds which have nophytotoxicity on rice plants and ordinary farm crops, when used atpractical application concentrations.

The present compounds of the formula (I) may be prepared according tothe following manner:

An alkali hydroxide, eg sodium hydroxide or potassium hydroxide, isdissolved in a suitable solvent, e.g. an alcohol such as methanol,ethanol or methyl cellosolve, water, N,N-dimethylformamide or dimethylsulfoxide. The resulting solution is saturated with hydrogen sulfide toform a solution of an alkali hydrosulfide represented by the formula(III). The thionophosphoric acid amidate represented by the formula (II)is added to the solution of the alkali hydrosulfide and the resultingmixture is heated while being stirred to complete dealkylation.Subsequently, the phosphoric acid salt in the form of a wet crystal or aviscous liquid is isolated and then condensed with the halogen compoundrepresented by the formula (V) in the presence or absence of a suitablesolvent, eg an alcohol such as methanol or ethanol, a ketone such asmethyl ethyl ketone or acetone, or water, whereby aphosphoroamidothiolate represented by the formula (I) can be obtainedeasily in a high yield.

The reaction temperature in the dealkylation varies depending on thekinds of the starting materials and the solvent, and is ordinarily thereflux temperature of the solvent used, and the reaction time is in therange of several hours to 10 and several hours. The reaction temperatureand time in the condensation reaction with the halogen compound are 30to C and 2 to 5 hours, whereby a desired compound can be obtained in ahigh yield.

Several examples of the starting materials used in the presentinvention, i.e. the phosphorothionoamidate, the alkali hydrosulfide andthe halogen compound, are shown below, but it is needless to say thatcompounds tions like in the case of ordinary organo-phosphoruspreparations, into any of such ordinarily adopted forms as emulsifiableconcentrates, wettable powders, oil sprays, dusts, aerosols, fumigantsand granules for soil application and seed-coating. Thus, the presentcompounds can be used in any required forms. Further, the presentcompounds may be used in admixture with one or more of other chemicalsand fertilizers to make the effects thereof broader and higher. Forexample, the compounds are mixed with organo-phosphorus typeinsecticides such as Sumithion (registered trade name for an insecticideproduced by Sumitomo Chemical Co.; the same shall apply hereinafter) andDimethoate, pyrethroid type insecticides such as allethrin andphthalthrin, organo-chlorine type insecticides such as BHC and DDT,carbamate type insecticides such as 3,-4-dimethylphenyl-N-methylcarbamate, 2-secbutylphenyl-N-methylcarbamate,S-methyIphenyl-N- methylcarbamate and 1-naphthyl-N-methylcarbamate,synergists, repellants, attractants and the like, whereby multi-purposecompositions can be prepared and, depending on the combinations,synergistic effects can also be expected.

In order to clarify the prominent characteristics and effects of thepresent compounds, typical test results are shown in the test examplesset forth below.

In the test examples, the present compounds are represented by theaforesaid exemplification numbers.

Test Example 1 Lethal effects (contact poison): Mottled kidney beanplants at the two-leaves stage,

which had elapsed 20 days after sowing, were parasitized with a largernumber of adults of twospotted red spiders Telranychus telarius). Thekidney bean leaves parasitized with said spiders were immersed for 1minute in a solution formed by diluting with water each of the presentcompounds in the form of wettable powders. Subsequently, water wassupplied so as not to wither the leaves. After 48 hours, the alive anddead of the spiders were observed by means of a magnifying glass and,from the mortality, the value of LC was calculated according to theFinneys simplified iconography. The results Test Example 2 Lethaleffects (insecticidal effects on smaller brown planthoppers, Laodelphaxstriatellus Fallen):

Rice seedlings (l5 20 cm in height), which has elapsed 15 days aftergermination, were immersed for 1 minute in an emulsion prepared bydiluting to a given concentration each of the present compounds in theform of emulsifiable concentrates which had been formulated according toExample 1. After air-drying, the seedlings were placed in a large testtube. Into the test tube were liberated 20 to 30 smaller brownplanthoppers, and the test tube was covered with a wire net. After 24hours, the mortality of the planthoppers were measured and, from themortality, the value of LC was calculated according to the Finneysiconography. The results obtained were as shown in Table 2.

Table 2.

Compound No. LC, (dilution times of active ingredient) Test Example 3Residual insecticidal effects:

Mottled kidney bean plants grown in a flower pot which had elapsed 20days after sowing were dusted, using a bell jar duster, with 3 kg/ 10ares of each of the present compounds in the form of 3 percent dusts.After the dusting, the plants were parasitized at intervals of severaldays with spider mite adults, and the mortality of the mites after 48hours from the dusting was investigated. The results obtained were asshown in Table 3.

' Control Text Example 4 Systemic effects:

Mottled kidney bean plants were grown to the twoleaves stage in a flowerpot of 9 cm in diameter. To the root portion of the plants were appliedin a proportion of 4 kg per 10 acres each of the present compounds inthe form of 3 percent granules. After 4 days, the mottled bean leaveswere parasitized with a large number of adults of two-spotted redspiders. Six days thereafter, the leaves were cut, and the alive anddead of the spiders were observed to calculate the mortality thereof.The results obtained were as shown in Table 4.

Table 4 W i and aphids, 100 g per tree of each of the present compoundsin the form of 5 percent granules was sprayed Compound Number of y to inthe form of a circle of 1 cm in radius. After days, 5 the number ofsurvival insects was counted to obtain 291 93.4 the results as set forthin Table 7. (2) 388 99.4 121 100.0 (6) 211 83.4 10 56l 73.8 Table 7 (12)620 92.7 (14) 315 100.0 10

Number of survival insects after 5 0,0-Dimethyl-S-(N-methyl- 631 90.8ays (per 500 leaves) carbamoyIJ-methyl phosphorodithioate" Compound N0.Moths Aphids 1) 0 0 Control 1 5 (g) 0 0 12.4 0 Test Example 5 (12) 34 MMice oral acute tox1c1ty: O O h S N Male mice having an average bodyWeight of about 123 g was orally admimstrated with an emulsion formedphosphorodithioare by d1lut1ng with water each of the present compounds20 Nonmeatmem 831 1n the form of emuls1f1able concentrates. After 48hours, the alive and dead of the mice were observed and, from themortality, the value of LD was calculated according to the Richfieldmethod. The results obtained were as shown in Table 5. f P 8 Mandarmorange frults, which had been parasit- TABLES ized with a large numberof Yaneno scales (Unaspis LDm yanenoensis Kuwana), were immersed for 1minute in Compound number -I e) a solution formed by diluting with watereach of the 1 200' present compounds in the form of 50 percent wettableE3" powders. After 2 weeks, the alive and dead of the scales igg wereobserved to calculate the mortality thereof. The (103: 93 resultsobtained were as shown in Table 8. 0,0-dlethyl-O-(4-r1ltrophenyl)phosphorothioate "m 6 Table 8 C 2H1:O SCII3(Compougd disclosed in Japanese patent publication No. CompoundMoi-rainy 4 100 Control. A i 40 (5) 8 l .2 (7) 73.4 Test Example 6 33'Rice plants at the offshoot stage which had elapsed0,0-Dimethyl-S-(N-methyL 63.4

30 days after planting were grown in a l/50,000 Wagner pot and parasitedwith 50 rice stem borer larvae immediately after hatching. Each of thepresent compounds in the form of 50 percent emulsifiable concentrateswas diluted with water to 200 times, and 6 cc per pot of the resultingemulsion was sprayed to the rice plants. After 3 days, the leaves of therice plants were broken, and the alive and dead of the larvae wereobserved to calculate the mortality thereof. The results obtained wereas shown in Table 6.

Table 6 Compound No. Mortality Control Test Example 7 To each rootportion of 5 years old apple trees grown in an orchard, which was beingattacked by leaf rollers 'carbamoyU-methyl phosphorodithioate ControlNumber of spots in non-treated Preventive area- Number of spots intreated value area (percent) Number of spots in non-treated area Table 9was calculated according to the Finneys iconography.

The results obtained were as shown in Table 1 1. Compound No.Activginggdient Preverzt ze value Table l l 5 (6) 500 Compound No. LCM,(p.p.m.) (7 do. 96.3 (a do. 92.8 (15) 2s (12) do. 89.3 (16) 23 17 47E81" do. 93.4 m (18) 31 l9 4 Non-treatment do. :21 i 45 Comm] TestExample 13 Test Example 10 15 Residual insecticidal effects:

A field of Chinese cabbages, which had elapsed 40 Mottled kldney beanplants grown m a flower pot days after sowing, was sectioned to areas of100 m wblch had lapsed 10 after Sowmg were dusted and each of thepresent compounds (I), (4) (8), using a bell ar cluster, with 3 kg/lOarcs of each of the and (14) in the form of 3 percent granules waspresent compounds in the form of 3 percent dusts. sprinkled over the fi61 d in a proportion of 3 kg per 10 20 After the dusting, the plantswereparasitized at interares. Over a period ofl month 300 eggs per 33 m2 ofvals of several days with spider mite adults, and the Prodenia lituraFabricius were attached onto the leaves moriamy 9 the mltes after 48 h()urs from the dusm lg of Said Cabbages every 5 days AS the result, noemer was investigated. The results obtained were as shown in gence ofProdenia litura Fabricius was observed at all Table during 2 monthsbefore harvest. Test Example 1 1 Mottled kidney bean plants at thetwo-leaves stage which had elapsed 10 days after sowing were parasitizedwith a large number of adults of two-spotted red spiders (Tetranychustelarius). The kidney bean leaves parasitized wth the said red spiderswere immersed for 1 minute in a solution formed by diluting with watereach of the present compound in the form of wettable powders, and thenwater was supplied so as not to wither the leaves. After 48 hours, thealive and dead of the red spiders were observed by use of a binocularmicroscope and, from the mortality, the value of LC was calculatedaccording to the Finneys simplified iconography. The results obtainedwere as shown in Table 10.

(Compound disclosed in Japanese patent publication No. 27,356/68)Control.

I Test Example 12 Lethal effects (insecticidal effects on smaller brownplanthoppers):

Rice seedlings (l5 20 cm in height), which had elapsed 15 days aftersowing, were immersed for l minute in an emulsion prepared by dilutingto a given concentration each of the present compounds in the form ofemulsifiable concentrates. After air-drying, the seedlings were placedin a large test tube. Into the test tube were liberated to smaller brownplanthopper adults, and the test tube was covered with a wire net. After24 hours, the mortality of the planthoppers was measured and, from themortality, the value of LC Mortality (percent) after- Compound number10o 90. 0 100 75. 0 47. 1 60. 0 100 100 93. 8 84. 6 98. 0 100 95. 3 100(19) 100 100 96.7 73. 2 0,0-tlimethyl- -(N-rncthy carbnmoyD- methylphospliororll hion e" 100 117.1 90.3 32.4

NH: O 3.1 7.8 "0

ofiao s-omo oH (Compound disclosed in J apa nese patent publication No.7 .357/ 68) Control.

Test Example 14 Systemic effects:

Mottled kidney bean plants were grown to the twoleaves stage in a flowerpot of 9 cm in diameter. To the root portion of the plants was appliedin a proportion of 4 kg per 10 area each of the present compounds in theform of 3 percent granules, and the plants were parasitized at intervalsof several days with two-spotted red spider adults. After 48 hours, theleaves of the plants were cut and taken up, and the alive and dead ofthe red spiders were observed by use of a binocular microscope. Theresults obtained were as shown in Table 13.

TABLE 13 Mortality (percent) mer- Compound number CHsO S-CH2C E CH 7(compound aisElEs'J in :lapanese patent publication No. 7,357/ 68) 2days 5 days 8 days 12 days Table 14 Compound No. Mortality0,0-Dimethyl-S-( N-methylcarbarnoyl-*methyl )-phosphorodithioate ControlTest Example 16 Tomato seedlings which had elapsed 1 month after sowingwere sprayed with an emulsion prepared by diluting with water to 1,000times each of the present compounds in the form of percent emulsifiableconcentrates. The tomato seedlings were cut and then placed in a glassPetri dish together with 28-spotted lady beetles (Epilachnavigintioctopunctata). After 48 hours, the alive and dead of the beetleswere observed to calculate the mortality thereof. The results obtainedwere as shown in Table 15.

Table Compound No. Mortality Sumithion* 88. l

Control Test Example 1 7 l8 23 Rice seedlings were grown to the 3-to 4-leaves stage in a flower pot of 9 cm in diameter and sprayed with anemulsion formed by diluting with water to 1,000 times each of thepresent compounds in the form of 50 percent emulsifiable concentrates.After airdrying, the rice seedlings were covered with a wire net, andsmaller brown planthopper adults were liberated into the wire net. After24 hours, the alive and dead of the planthoppers were observed tocalculate the mortality thereof. Further, smaller brown planthopperadults were freshly liberated in the wire net at intervals of severaldays to examine the residual effect of each of the present compounds.The results obtained were as shown in Table 16.

Table 16 Mortality Compound No. After After After After 1 day 4 days 7days ll days (15) 93.3 92.0 86.6 26.7 (16) I000 86.6 74.0 29.6 (l8)100.0 90.0 13.3 l0.0 (19 96.2 92.6 71.4 29.6 3,4-Dimethylphenyl-* 6.4

N-Methylcarbarnaie 93.1 70.0 10.0

' Control Test Example 18 Mice oral acute toxicity: Male mice having anaverage body weight of about 20 g were orally administrated with anemulsion formed by diluting with water each of the present compounds inthe form of emulsifiable concentrates. After 48 hours, the alive anddead of the mice were observed to calculate the value of LlD accordingto The Richfield method. The results obtained were as shown in Table 17.

TABLE 17 LDso Compound number (mg./kg.)

(15) i 16) 50 (17) c (18) 50 (ll!) 600 (20) 1,0000,0-(llcthyl-()-(4-nlLmphunyl)-pllosphorothloate.. 6

CHaO S-CH C CH (Compound disclosed in Japanese patent publication No.7,357/68) 021150 SOH= (Compound disclosed in Japanese patent publicationNo. 21 11..

Test Example 19 Preventive effects on rice blast Rice plants (varietyWaseasahi), which had been cultivated to the three leaves stage in aflower pot of 9 cm in diameter, were pr .d..vvit ml. r PQtQf a QE B E I!term by luting to a given concentration each of the present compounds inthe form of emulsifiable concentrates. After 4 hours, the plants wereinoculated with a spore suspension of rice blast fungus. Three daysthereafter, the number of spots generated was counted to investigate thefungicidal effect of each compound. The results obtained were as shownin Table 18. All the present compounds displayed quite excellent effectsas compared with the known analogous compound.

The preventive value was calculated according to the same equation as inTest Example 9.

Preparation of emulsifiable concentrate:

According to the table shown below, each compound was thoroughly mixedwith the solvent and the emulsifier in this order to obtain ahomogeneous emulsifiable concentrate. In application, the emulsifiableconcentrate was diluted with water and the resulting emulsion wassprayed.

Active ingredient Binder Extender Compound (4) 2 Sodium lignin 1 Clay 97sulfonate Compound (12) 5 do. 2 do. 93

TABLE 18 I 7 V V Example 4 w gfiglgi g gg Preparation of dust: Comp undnumber (p-n (p 1 According to the table shown below, each compound 1,00092.6 was dissolved in a small amount of acetone and thor- 33:2 oughlymixed with 200 mesh talc, and then the acetone 1 000 n 2 was removed byvaporization to obtain a dust. The dust was dusted as it was.

CzHsO SCH3 l5 ggfigglzl g: ifg g j patent Active ingredient ExtenderNon-treatment 0. 0 Compound (7) 2 Talc 98 Do. 4 do. 96

Control H g V I 2O The present invention illustrated in further detailbelow with reference to examples, but it is needless to say that theinvention is variable within a wide scope without being limited only tothese examples. lq

Example 1 Preparation of emulsifiable concentrate: According to thetable shown below, each compound was thoroughly mixed with the solventand the emulsifier in this order to obtain a homogeneous emulsifiable'concentrate. In application, the emulsufiable concentrate was dilutedwith water and the resulting emulsion was sprayed.

Active ingredient Solvent Emulsifier Compound (I5) 50 Xylene Sorpol 202020 Compound (19) 20 Cyclohexanone Sorpol 2492 30 Active ingredientSolvent Emulsifier Compound (1) 50 Xylene 30 Sorpol 2020 20 Compound (5)20 Cyclohexanone 50 Sorpol 2492 30 x p 2 Example 6., V Preparation ofwettable powder: 50 Preparation of wettable powder:

40 Parts of the compound (9) was thoroughly mixed with 5 parts of Sorpol5029 (registered trade name for an emulsifier produced by Toho ChemicalCo.). The resulting mixture was dropped in parts of 200 mesh talc, whilesufficiently stirring the talc in a mortar, to obtain a wettable powder.In application, the wettable powder was diluted with water and theresulting solution was sprayed.

Example Preparation of granule:

According to the table shown below, each compound was thoroughly mixedwith the binder and the extender in this order. After kneading with asmall amount of water, the resulting mixture was granulated by means ofa granulator and then dried to obtain a granule. In application, thegranule was sprinkled as it was.

40 Parts of the compound (23) was thoroughly mixed with 5 parts ofSorpol 5029. The resulting mixture was dropped in 55 parts of 200 meshtalc, while sufficiently stirring the tale in a mortar, to obtain awettable powder. In application, the wettable powder was diluted withwater and the resulting solution was sprayed.

Example 7 Preparation of granule:

According to the table shown below, each compound was thoroughly mixedwith the binder and the extender in this order. After kneading with asmall amount of water, the resulting mixture was granulated by means ofa granulator and then dried to obtain a granule. In application, thegranule was sprinkled as it was.

Active ingredient Binder Extender Compound (18) 2 1 Clay 97 Sodiumlignin sulfonate Compound (2!) 5 2 do. 93

Example 8 the same manner as in Example 9 to obtain 9.8 g of 10O-methyl-S-propargyl-N-allyl phosphorothioamidate in P t' f d r;

the form of a reddish brown 011, u 1.5140.

According to the table shown below, each compound was dissolved in asmall amount of acetone and thoroughly mixed with 200 mesh talc, andthen the acetone was removed by vaporization to obtain a dust. Inapplication, the dust was dusted as it was.

Elementary analysis:

Calculated Found (for c,1-1 ,,No,Ps

P 15.09 l4.69 5 15.59 15.26 Active Extender N ingredient Compound (21) 2Talc 98 Compound (24) 4 Example 1] Example 9 Synthesis of compound (9):

25 To a methyl cellosolve solution of potassium hydro- Synthesis ofcompound (1): sulfide prepared from 100 ml of methyl cellosolve, 12.2

11.2 g of potassium hydroxide was dissolved in g of potassium hydroxideand hydrogen sulfide was 100 ml of methyl cellosolve, and the resultingsolution added 41.8 g of 0,0-diethyl-N-allyl phosphorothwas saturatedunder cooling with hydrogen sulfide ionoamidate, and the resultingmixture was stirred at to prepare a methyl cellosolve solution ofpotassium 95 to 100C for 7 hours'. The mixture was treated in hydrosulfide. To this solution was added at room. the same. manner as inExample 9 to obtain 39.5 g of temperature 36.2 g of 0,0-dimethyl-N-allylphos potassium O-ethyl-N-allyl phosphorothioamidate in thephorothionoamidate, and the resulting mixture was. form of a WetlableWhite y i d at 95 to 100C fo 5 h 10.9 g of the thus obtainedthiophosphoric acid salt Subsequently, the solvent was removed underreand g of methyl iodide were irred at 45 to 50C duced pressure, theresidue was mixed with acetone f 1 h of 50 ml of ethyl alcohol-Subsequently, the

and freed from insolubles, and then the acetone was rereaction liquidtreated in the Same manner as in moved under reduced pressure.Thereafter, the residue Example 9 9 obthlh g of y y l was dissolved inwater and then washed with toluene phosphorothloamldate the form Ofa PYellQW 011,

From the aqueous layer, water was removed under re-} 40 0' ducedpressure to obtain 40.2 g of potassium o-methyl-I N-allylphosphorothioamidate in the form of a pale yellow viscous liquid. I

10.3 g of this salt was dissolved in 50 ml of methyl alcoho], and theresulting solution was charged with 7.5 Elementary analysi-SI g ofmethyl iodide and stirred at to C for 1 hour. Calculated FoundSubsequently, the solvent was removed under reduced (for CGHHNOJSV)pressure, the residue was charged with water and chlo- P 15.86 [544roform, and the chloroform layer was drid with anhy- 5 16.39 16.41 droussodium sulfate. Thereafter, the chloroform was 50 N removed underreduced pressure to obtain 8.7 g of 0,8- diemthyl-N-allylphosphorothioamidate in the form of a pale yellow oil, H025 1.5032.

Example 12 515mm analysis 55 Synthesis of compound (5):

ca c ed pound To a methyl cellosolve solution of sodium hydrosul (for c,H,,N0,PS fide prepared from 50 ml of methyl cellosolve, 4.0 g of p M1017-07 sodium hydroxide and hydrogen sulfide was added 18.] 1.: l g of0,0-dimethyl-N-allyl phosphorothionoamidate, 5 and the resulting mixturewas stirred at to C for Example 10 5 hours. After cooling to roomtemperature, the mixture was charged with 13.2 g of allyl bromide andthen Synthesis of compound (4); stirred at 55 to 60C for 2 hours.Subsequently, the re- A mixture comprising 10,3 g f p tas i m O. th 65action liquid was treated in the same manner as in Ex- N-allylphosphorothioamidate and 6.5 g of propargyl mp 9 to b n 7-5 g 0f0-methyl-S-allyl-N-allyl bromide was stirred and refluxed for 2 hours in50 ml phosphorothioamidate in the form of a pale yellow O of methylalcohol. The reaction liquid was treated in 0 039- Elementary analysis:

Calculated Found (for C,H NO PS) P 14.94 14.79 S 15.47 15.30 N 6.76 6.59

EXAMPLE 13 Synthesis of compound (2):

A mixture comprising 10.3 g of potassium O-methyl- N-allylphosphorothioamidate and 6.0 g of ethyl bromide was stirred under refluxfor 3 hours in 50 ml of acetone. Subsequently, the mixture was treatedin the same manner as in Example 9 to obtain 8.3 g of O-methyl-S-ethyl-N-allyl-phosphorothioamidate, in the form of a paleyellow 011, n,, 1.4930.

Elementary analysis:

Calculated Found (for C H NO S) P 15.86 15.82 S 16.42 16.71 N 7.18 6.78

EXAMPLE 14 Synthesis of compound (3):

A mixture comprising 19.0 g of sodium O-methyl-N- a11y1phosphorothioamidate and 6.8 g of (n)-propy1 bromide was stirred underreflux for 3 hours in 50 ml of methyl alcohol. The mixture was treatedin the same manner as in Example 9 to obtain 7.6 g ofO-methyl-S-(n)-propyl-N-allyl phosphorothioamidate in the form of a paleyellow oil, n 1.4853.

Elementary analysis:

Calculated Found (for C H NO PS) P 14.80 14.79 S 15.32 15.47 N 6.69 6.37

EXAMPLE 15 Synthesis of compound (6):

A mixture comprising 10.3 g of potassium O-methyl- N-allylphosphorothioamidate and 5.0 g of methallyl chloride was stirred underreflux for 2 hours in 50 ml of methyl alcohol. The mixture was treatedin the same manner as in Example 9 to obtain 9.1 g of O-methyl-S-methallyl-N-allyl phosphorothioamidate in the form of a yellow oil, n1.5018.

Elementary analysis:

Calculated Found (for C H NO PS) P 14.80 14.79 S 15.32 15.51 N 6.69 6.37

EXAMPLE 16 Elementary analysis:

Calculated Found (for C H CINOJS) P 12.11 12.08 5 12.54 12.67 N 5.485.36 C1 13.86 13.57

EXAMPLE 17 Synthesis of compound (8):

A mixture comprising 10.3 g of potassium O-methyl- N-allylphosphorothioamidate and 5.8 g of 1,3- dichloropropene was stirred underreflux for 2 hours in 50 m1 of methyl alcohol. Thi mixture was treatedin the same manner as in Example 9 to obtain 9.1 g of O-methy1-S-(3-chlor0-2-propenyl)-N-a11y1 phosphorothioamidate in the formof a pale yellow oil, nlffj 1.5 199.

Elementary analysis:

' Calculated Found (for C-,l-1 C1NO,PS)

P 12.76 12.77 S 13.21 13.30 N 5.77 5.57 CI 14.61 14.39

EXAMPLE 18 Synthesis of compound (10):

A mixture comprising 1 1.0 g of potassium O-ethyl-N- allylphosphorothioamidate and 7.1 g of ethyl bromide was stirred at to C for3 hours in 50 ml of ethyl alcohol. The mixture was treated in the samemanner as in Example 9 to obtain 9.5 g of O,S-diethyl-N-al1y1phosphorothioamidate in the form of a yellow oil, n 1.4889.

Elementary analysis:

Calculated Found (for C,H,.,NO,PS)

P 14.80 14.53 S 15.32 15.58 N 6.69 6.31

EXAMPLE 19 Synthesis of compound (1 l):

Elementary analysis:

Calculated Found (for C H NO PS) P 13.87 13.28 S 14.36 14.51 N 6.27 5.68

EXAMPLE Synthesis of compound (12):

A mixture comprising 1 1.0 g of potassium O-ethyl-N- allylphosphorothioamidate and 6.5 g of propargyl bromide was stirred at 55 to60C for 2 hours in 50 ml of ethyl alcohol. The mixture was treated inthe same manner as in Example 9 to obtain 9.8 g ofO-ethyl-S-propargyl-N-allyl phosphorothioamidate in the form of areddish brown 011, n 1.5091.

Elementary analysis:

Calculated Found (for CBH14NO2PS) P 14.12 13.64 S 14.62 15.16 N 6.396.08

EXAMPLE 21 Synthesis of compound (13):

A mixture comprising 1 1.0 g of potassium O-ethyl-N- allylphosphorothioamidate and 6.5 g of allyl bromide was stirred under refluxfor 2 hours in 50 ml of ethyl alcohol. The mixture was treated in thesame manner as in Example 9 to obtain 10.0 g of O-ethyl-S-allyl-N-allylphosphorothioamidate in the form of a yellow oil, n 1.4969.

Elementary analysis:

Calculated Found (for C H NO Ps) P 13.99 13.70 S 14.46 14.58 N 6.33 6.10

EXAMPLE 22 Elementary analysis:

Calculated Found (for C,.H,,,N0 PS EXAMPLE 23 Synthesis of compound(18):

1 1.2 g of potassium hydroxide was dissolved in ml of methyl alcohol,and the resulting solution was saturated under cooling with hydrogensulfide to prepare a methyl alcohol solution of potassium hydrosulfide.To this solution was added at room temperature 43.0 g of0,0-dimethyl-N-methylthioethyl phosphorothionoamidate, and the resultingmixture was stirred under reflux for 4 hours. Subsequently, the solventwas removed under reduced pressure, the residue was charged with acetoneand freed from insolubles, and then the acetone was removed underreduced pressure. Thereafter, the residue was dissolved in water andthen washed with toluene. From the aqueous layer, water was removedunder reduced pressure to obtain quantitatively potassiumO-methyl-N-methylthioethyl phosphorothioamidate in the form of awettable pale yellow crystal. 12.0 g of this salt was dissolved in 50 m1of methyl alcohol, and the resulting solution was charged with 6.3 g ofpropargyl bromide and stirred under reflux for 2 hours. Subsequently,the solvent was removed under reduced pressure, the residue was chargedwith water and chloroform, and the chloroform layer was dried withanhydrous sodium sulfate. Thereafter, the chloroform was removed underreduced pressure to obtain 9.9 g ofO-methyl-S-propargyl-N-methylthioethyl phosphorothioamidate in the formof a reddish brown oil, n 1.5457.

Elementary analysis:

Calculated Found (for C,H N0 P 2) P 12.94 12.97 S 26.79 26.31 N 5.855.73

EXAMPLE 24 and 6.3 g of propargyl bromide were stirred under re-- fluxfor 2 hours in 50 ml of acetone. The reaction mixture was treated in thesame manner as in Example 23 to obtain 7.8 g ofO-methyl-S-propargyl-N-cyanoethyl phosphorothioamidate in the form of areddish brown oil, n 1.6188.

Elementary analysis:

2 hours in 50 ml of methyl alcohol. Subsequently, the mixture wastreated in the same manner as in Example 23 to obtain 10.2 g ofO-methyl-S-propargyl-N-ethyl- Calculated Found (fm C1H11N202Ps) 5thioethyl phosphorothioamidate in the form of a redp 14 19 1 9 bl'OWllOil, 11 I 5 14.68 14.23 N 12.84 12.51

Elementary analysis: EXAMPLE 25 Calculated Found Synthesis of compound(22): (for CaHmNoaPSz) To a methyl cellosolve solution of potassiumhydro- P 12.23 12.11 sulfide prepared from 100 ml of methyl cellosolve,1 1.2 f g :33 g of potassium hydroxide and hydrogen sulfide was i added42.6 g of 0,0-dimethyl-N-methoxypropyl phosphorothionoamidate, and theresulting mixture was stirred at 95 to 100C for 2 hours. The mixture wasEXAMPLE 28 treated in the same manner as in Example 23 to obtainquantitatively potassium O-methyl-N-3-methoxypropyl 2O i of compoulull 9f otassi m phosphorothioamidate in the form of a pale yellow vismm wecompn'smg g 0 u Cons liqum O-methyl-N-3-methoxypropylphosphorothionoami- 11.9 g of the thus obtained thiophosphoric acid saltdate and g of pmpargyl bromlde a Stu-red under and 73 g of methyl iodidewere Stirred at 0 to SOOCV reflux for 2 hours in 50 ml of methylalcohol. Subsefor 1 hour in 50 m] of methyl alcohoL Subsequently, 25quently, the mixture was treated in the same manner as the reactionmixture was treated in the same manner as Example 23 to obtain g of 'fly in Example 23 to obtain 8.9 g of O,S-dimethyl-N- p P y yp pyphvsphowthwamldate methoxypropyl phosphorothioamidate in the form ofthefofm of l h bro p T1023 8' a colorless transparent oil, n 1.4872. I

' Elementary analysis:

Elementary analysis; gi gg jgg Found Calculated Found(%) 2 1:2? 1:12: P14.52 14.46 N 590 5 15.03 14.87 N 6.57 6.46

40 EXAMPLE 29 Synthesis of compound (21 EXAMPLE 26 A mixture comprising12.0 g of potassium Synthesis f compound 19 O-ethyl-N-ethylthioethylphosphorothioamidate and A mixture comprising 20 g f potassium 6.3 g ofpropargyl bromide was stirred under reflux for methyl Nmethyltl-lioethy] phosphorothioamidate 2 hours in ml of ethyl alcohol.Subsequently, the and 65 g f n bromide was Stirred at for 4 mixture wastreated in the same manner as 1n Example hours. A separated oilysubstance was treated in the to obtam g P ofethylfs'propargyl'Nethyl'same manner as in Example 23 to obtain 95 g of th1oethylphosphorothioamldate 1n the form of aredmethyl-S-allyl-N-methylthioethyl phosphorothioamibrown date in theform of a yellow oil, 11,, 1.5305. 2

Elementary analysis:

Elementary analysis: Calculated Found (for c,,11,,.No,1 s,) CalculatedFound (for C,H, NO PS P 11.58 11.73 s 23.99 23.65 P 12.83 12.69 N 598 526.57 26.36 N 5.81 5.75

EXAMPLE 3O EXAMPLE 27 Synthesis of compound (20):

A mixture comprising 12.0 g of potassium Synthesi f mp n 5):O-me'thyl-N-methylthioethyl phosphorothioamidate A mixture comprising12.7 g of potassium 5 and 6.0 g of ethyl bromide was stirred at 60C for3 O-methyl-N-ethylthioethyl phosphorothioamidate and 6.3 of propargylbromide was stirred under reflux for hours in 50 ml of methyl alcohol.Subsequently, the mixture was treated in the same manner as in Example23 to obtain 8.5 g of O-methyl-S-ethyl-N-methylthioethylphosphorothioamidate in the form of a yellow oil, n 1.5197.

Elementary analysis:

Calculated Found (for C H NO PS EXAMPLE 31 Synthesis of compound (24): Amixture comprising 12.0 g of sodium O-ethyl-N-ethylthioethylphosphorothioamidate and 10.2 g of 2.3-dibromopropene was stirred underreflux for 2 hours in 50 ml of ethyl alcohol. Subsequently, the mixturewas treated in the same manner as in Example 23 to obtain 13.0 g ofO-ethyl-S-2-bromopropenyl-N- ethylthioethyl phosphorothioamidate in theform of a yellow oil, n 1.5627.

Elementary analysis: 4

Calculated (for C H BrNO PS P 8.89 8.53 S 18.41 18.27 N 4.02 3.7l

EXAMPLE 32 Synthesis of compound (23):

A mixture comprising 12.0 g of potassium O-methyl-N-methylthioethylphosphorothioamidate and 5.7 g of 1,3-dichloropropene was stirred underreflux for 3 hours in 50 ml. of methyl alcohol. Subsequently, themixture was treated in the same manner as in Example 23 to obtain 11.3 gof O-methyl-S-3- chloropropenyl-N-methylthioethyl phosphorothioamidatein the form of a yellow oil, n 1.5528.

Elementary analysis:

Calculated Found (for C,H, ClNO PS- P 11.23 11.45 S 23.26 23.58 N 5.085.31

Found What is claimed is: 1. An amidothiol phosphoric acid ester havingthe formula,

wherein R is methyl, ethyl or propyl, R is a C -C alkenyl, a C -C,alkylthioalkyl, a C C alkoxyalkyl or u C C, cyanoalkyl, and A is a C,C,,alkyl, a C -C 5. A compound of the formula,

6. A compound of the formula,

A sqmpqsa 9f h f mly a 9 A compoundof the formula,

11. A compound 12. A compound of the formula,

13. A compound of the formula,

2. An amidothiol phosphoric acid ester of claim 1, wherein R1 is methylgroup.
 3. An amidothiol phosphoric acid ester of claim 1, wherein R2 isallyl group.
 4. A compound of the formula,
 5. A compound of the formula,6. A compound of the formula,
 7. A compound of the formula,
 8. Acompound of the formula,
 9. A compound of the formula,
 10. A compound ofthe formula,
 11. A compound of the formula,
 12. A compound of theformula,
 13. A compound of the formula,